Process for the dyeing of polyamide fibers



United States Patent 3,467,485 PROCESS FOR THE DYEING 0F POLYAMIDE FIBERS Alfred Schaeuble, Riehen, Ernst Adolf Ranchle, Base],

and Willi Leutenegger, Basel-Land, Switzerland, assignors to J. R. Geigy A.G., Basel, Switzerland No Drawing. 'Continuation-in-part of application Ser. No. 276,065, Apr. 26, 1963, which is a continuation-in-part of application Ser. No. 214,510, Aug. 3, 1962. This application May 13, 1964, Ser. No. 367,235 Claims priority, application Switzerland, May 3, 1962, 5,312/ 62; May 21, 1963, 6,324/ 63 Int. Cl. D06p 3/24; C09b 67/00 US. Cl. 8-54 13 Claims ABSTRACT OF THE DISCLOSURE Processes are provided for the dyeing of polyamide fibers as well as dye liquors suitable for these processes. The provided processes for coloring polyamide fibers comprise:

(a) impregnating the said fibers by padding, printing, coating or spraying with a thickened liquor containing acid wool dyestufI and a thickener, at a temperature below the drawing temperature of the dyestuff, whereby the dyestuff is deposited on the fibers without drawing on to them substantively, and then heating the impregnated fibers to at least 80 in a humid medium without introduction of steam thereinto, or

(b) impregnating the said fibers in the same manner as described under (a) and then steaming the impregnated fibers in a humid medium, or

(c) impregnating the said fibers by padding, vigoureux printing, coating or spraying, and then passing the impregnated fibers through a hot acid shock bath, or

(d) impregnating the said fibers in the same manner as under (c) and then steaming the impregnated fibers in a humid medium and subsequently passing them through a hot acid shock bath.

The impregnating material comprises a thickened aqueous liquor or a thickened printing paste containing an acid wool dyestutf and a thickener in addition to:

(l) as color transfer agent for transferring the said acid wool dyestuff during fixing from the deposit on the fiber into the interior of the fiber, an effective amount of a water-soluble salt of a saturated aliphatic monocarboxylic fatty acid having 8 to 14 carbon atoms with a monoto divalent cation selected from the group consisting of alkali metal ion, ammonium ion, lower alkyl-substituted ammonium ion, lower alkoxy-alkyl substituted'am monium ion, morpholinium ion, piperidinium ion, and hydroxy-(lower alkyl)-substituted ethylene-diammoniurn ion, and

(2) a polyglycolether selected from the group consisting of fatty alcohols and saturatedfatty acids having 8 to 14 carbon atoms, each mol of which is condensed with 4 to 12 equivalents of ethylene oxide.

The invention also provides impregnation liquors for the dyeing and printing of the polyamide fibers as well as Patented Sept. 16, 1969 "ice compositions for use as dyeing auxiliaries in thickened dye liquors.

This application is a continuation-in-part of our pending application Ser. No. 276,065 filed Apr. 26, 1963, now abandoned, which is a continuation-in-part of our application Ser. No. 214,510 filed Aug. 3, 1962 (now abandoned).

The present invention concerns processes for the dyeing of polyamide fibers as well as dye liquors suitable for these processes.

The continuous dyeing of polyamide fibers is known. A known process consists, for example, in impregnating wool with a preferably thickened aqueous solution of acid wool dyestuffs at temperatures under the drawing temperature of these dyestuffs, then drying the impregnated goods, passing them through a hot acid bath to fix the dyestuff (acid shock method) and then rinsing. As this process has considerable disadvantagese.g. it produces uneven dyeingsit has not attained any practical importance.

As a further development of this process, the addition of carriers to the impregnation liquors has already been suggested. As such, water-soluble condensation products of fatty acids having 8 to 14 carbon atoms or of mixtures of such acids with 2 equivalents of dialkanolamine have I proved to lead to the best hitherto attainable results. Such condensation products are known as Kritchevsky bases and are obtained according to the process described in the US. Patent No. 2,089,212.

However, the use of these impregnation liquors has also a number of disadvantages. Above all, such impregnation liquors are not stable, as often after a few hours for no apparent external reason they separate irreversibly into two phases, one poor in auxiliaries and the other containing the main amount of dyestufi' and auxiliaries. This phase formation in the'impregnation liquor makes level dyeing, particularly of large batches, more difficult.

The tendency to phase formation of impregnation liquors has become the standard of their usefulness. However, practical experience has shown that the impregnation liquors of the known process described only produce useful dyeings when the content of dyestuff, electrolytes and auxiliaries is very carefully calculated. Phase formation is particularly strongly dependent on the salt content of the impregnation liquor. But the inclusion of electrolytes in the liquor is unavoidable if, in the continuous process, for example," carbonized and neutralized wool is used which has not been sufficiently carefully rinsed. Such factors adversely influence the evenness of the dyeings obtained by the known process. Finally, if the dyestuff is fixed by passing the impregnated goods through a hot acid bath, previous drying of the goods saturated with the impregnation liquor has proved to be'nece'ssary in order to avoid undesirable bleeding in the acid bath.

It has now been found that, contrary to general opinion, surprisingly suitable impregnation liquors for the continuous dyeing of natural and synthetic polyamide fibers are obtained if auxiliaries are added as carriers to aqueous dyestuif solutions which neither on longer standing nor on alteration of the electrolyte content impart a phase formation tendency within the usual technical margins to these liquors.

In a first process according to the invention, thickened aqueous solutions of acid wool dyestuffs and thickening agent are used which, as substantial color transfer agent (carrier), contain a mixture of (a) an active amount of soluble salts of saturated aliphatic monocarboxylic acids having 8 to 14 carbon atoms, (b) polyglycol others which are the condensation products of fatty alchols or fatty acids having 8 to 14 carbon atoms, with ethylene oxide in such amount that the polyglycol ethers contain 4 to 12 ether groups; optionally, the aforesaid color transfer agent may contain other auxiliaries.

Natural or synthetic polyamide fibers are impregnated with such liquors at temperatures which are below the drawing temperature of these dyestuifs and the dyeing of the fiber materials so treated is completed by a heat treatment in a humid medium (steam), without or combined with the action of acid (acid shock bath) and then rinsing, preferably in cold water.

Whereas additions of non-foaming anion active dispersing agents from the class of aromatic sulfonic acids or their water-soluble salts, in particular fl-tetrahydronaphthalene sulfonic acid or a mixture of aand fi-tetrahydronaphthalene sulfonic acid or of their water soluble salts are necessary to maintain the dye liquor in a monophase state when Kritchevsky bases are used, the present process can be performed, completely unexpectedly, without such additions, thus rendering it simpler and more economical to carry out in practice.

It is a particular advantage of the process according to the invention that uniform dyeings are obtained even when large batches are being dyed and, furthermore, that the hot acid shock bath can be applied directly to the wet impregnated goods which have only been freed mechanically from excess impregnation liquor, for instance by wringing, but retain a content of the liquor of at least about 40% calculated on the weight of the dry goods, without any drying of the goods between the dye bath and the acid shock bath, and that this can be effected without the occurrence of any permanent bleeding and corresponding loss of dyestuff from the dyed fibers, as it occurs when Kritchevsky bases are used and when no intermediate drying is applied before the acid shock bath. The drawing temperatures of the dyestuffs used, i.e. the temperature at which 60-70% of the amount dyestulf employed in the dyebath has drawn onto the fiber in one minute, is at least 70 C. or higher and preferably 90 to 100 C. In the process according to the invention, the impregnation of the fiber materials with the dyestuff must be performed at a temperature below this drawing temperature and above room temperature (20 C.), preferably in the range of 40 to 70 C., and at a pH of at least 5 and up to 11 and even higher, preferably about 6.5 to 8. At a pH lower than 5, the impregnation liquor loses its homogeneous nature (monophase), with ensuing drawbacks of multiphase impregnation as set forth above.

The process according to the invention is excellently suitable for the continuous dyeing of polyamides, particularly of wool, with a one-phase dyebath of the abovedefined pH, depending on the alkali-resistance of the fiber being dyed. In contrast thereto, dyebaths containing as carrier solely soluble salts of saturated aliphatic monocarboxylic acids as defined under (a), supra, can be used for dyeing the same above-described fibers only in a pH range of 6.5 and higher.

The invention thus constitutes an important advance in the art of dyeing nitrogen-containing fibers, and especially of wool on the one hand because, as is well-known, wool is most advantageously dyed in a pH range below 6 and as closely to the isoelectric point of wool as possible. Thanks to the instant invention, this desirable pH range can be approached down to a pH value of about 5. Dyebaths according to the invention should not be used below this pH value because the one-phase system would break down.

As component (a) of the mixed carrier in the dyebaths according to the invention, salts of suitable saturated aliphatic carboxylic acids are used, for example, alkali salts such as lithium, sodium or potassium salts, ammonium salts or N-alkylor N-hydroxyalkylammonium salts or alkoxyalkyl-substituted ammonium salts of caprylic acid, pelargonic acid, capric acid, lauric acid or myristic acid, or of the acid mixtures all comprehended by the inclusive term coconut oil fatty acids, or of decyloxyacetic acid, lauryloxy acetic acid, decylthioacetic acid or of laurylthioacetic acid. Examples of N-substituted ammonium salts of the acids mentioned are derived from primary, secondary or tertiary amines, e.g. from monoalkylamines such as methyl, ethyl, propyl or isopropyl amine, from hydroxyalkylamines such as fl-hydroxy-ethyl, or [3- or 'y-hydroxypropyl amine, from dialkylamines such as diethylamine, and, in particular, from bis-(hydroxyalkyl)-amines such as bis-(fi-hydroxyethyl)-amine or bis-('y-hydroxypropyl)-amine or from his (5, dihydroxypropyl)-amine, from N alkyl N- (hydroxyalkyl)-amines such as N-methylor N'ethyl- N-(B-hydroxyethyD-amine or N-methylor N-ethyl-N- (y-hydroxypropyD-amine, also from strong cyclic nitrogen bases such as morpholine, from trialkylamines, particularly from tri-(hydroxyalkyl)-amines, e.g. from tri- (B-hydroxyethyl-amine, from N-alkyl bis N (hydroxyalkyl)-amines such as N-rnethylor N-ethyl-N,N-bis-(B hydroxyethyl)-amine or N-methylor N-ethyl-N,N-bis- (B- or 'y-hydroxypropyl)-amine or N-ethyl-N,N-bits- (fin-dihydroxypropyl)-amine, or from diamines, i.e. hydroxyalkylated diamines such as tetrahydroxyethylethylenediamine. The alkali, alkylammonium or hydroxyalkylammonium salts, mainly the (B-hydroxyethyD- ammonium salts, bis-(fi-hydroxyethyl)-ammonium salts, bis ('y hydroxypropyl) ammonium salts, methyl (B- hydroxyethyl)-ammonium salts, methyl-bis-(fl-hydroxyethyl) ammonium salts or methyl (5, dihydroxypropyl)-ammonium salts of coconut oil fatty acids have proved to be particularly good.

As component (b) of the mixed carrier in the dyebaths according to the invention, namely reaction products of 4 to 12, preferably 5 to 10 equivalents of ethylene oxide with one equivalent of, e.g., octyldecyl-, dodecyl-, tetradecyl-alcohol or with one equivalent of one of the fatty acids mentioned above are used as polyglycol others.

The other auxiliaries mentioned under b) which may be present in the impregnation liquors are essentially the following: inorganic salts such as sodium chloride or sodium sulfate, particularly also chromic acid salts when metallizable dyestulfs are used, also lower alkanoic acids such as acetic acid, but principally amides of saturated aliphatic monocarboxylic acids having 8 to 14 carbon atoms which are derived from primary and secondary amines having at least one low hydroxyalkyl group. When such amides are present in the liquor, the weight ratio of amides to mixture of the water-soluble salts and polyglycolethers must be about 1:2 or less. Suitable amides are derived, for example, from the higher fatty acids and mono-hydroxy-lower alkylamines described above, e.g. B- hydroxyethylamine, y-hydroxypropylamine or fi,'y-dihydroxypropylamine, bis-(hydroxy-lower alkyl)-arnines such as bis-(fl-hydroxyethyD-amine or bis-('y-hydroxypropyD- amine or bis-(a-methyl-B-hydroxyethyl)-amine, N-alkyl- N-(hydroxy-lower alkyl)-amines such as N-methylor N- ethyl-N-(fl-hydroxyethyD-amine or N-methylor N-ethyl- N-( -hydroxypropyl)-amine as well as the lower alkyl ethers, particularly the methyl or ethyl ethers, of the hydroxy-lower alkylamines mentioned such as p-methoxyor fl-ethoxyethylamine or 'y-methoxyor 'y-ethoxy-proplyamine.

Lower as used in this specification and the appended claims in connection with an aliphatic radical such as an alkyl, alkoxy or alkanoyl radical means a radical from 1 to 4 carbon atoms.

The acid wool dyestuffs usable according to the invention, i.e. those which are present as anions in a neutral to weakly acid dyebath, can be of any class of dyestuffs desired. For example, they can be metal-free, heavy-metal containing or metallizable monoor poly-azo dyestufis, formazane, anthraquinone, phthalocyanine or nitro dyestuffs. The process according to the invention is suitable in particular for dyeing with metallizable azo dyestuffs, this in the presence of soluble chromic acid salts, or with metal-containing azo dyestuffs, preferably with monoazo dyestuffs which contain 2 molecules of azo dyestuff bound to one heavy metal atom such as chromium or cobalt.

The thickeners used are the products known in textile printing, in particular the water soluble salts of alginic acids. However, also cellulose derivatives such as methyl cellulose or soluble salts of carboxymethyl cellulose can be used. Sufficient amounts of thickener should be used in the dye liquors according to the invention to impart to those liquors a viscosity of about 35 to 75 centipoises.

Both natural and also synthetic polyamide fibers can be dyed according to the invention. Examples of natural polyamides are wool and silk; examples of synthetic polyamides are nylon, Perlon (Perlon-Warenzeichenverband, Registered Company, Frankfurt am Main, Germany), Rilsan (Socit Organico, Paris, France) or Grilon (F. Emser Werke, Ems, Switzerland), etc. Sometimes a drying of the impregnated synthetic polyamides under thermd fix conditions, i.e. for example at a temperature of 150- 250 is advantageous. The dyeing process according to the invention is employed chiefly for W001. This is finished under more mild conditions, e.g. in a hot to boiling acid bath or by steaming.

The polyamide material can be dyed according to the invention in any form desired, for example in the form of flakes, slubbing, yarn or fabrics, the latter two after the conventional chlorination prior to printing, or even without such chlorination. Mixed fibers such as cellulose fibers mixed or encased with polyamides, particularly also in the form of mixed fabrics, can also be dyed, in particular mixed fabrics of wool and polyester fibers such as cellulose acetate, cellulose triacetate and, particularly, polyterephthalic acid diol ester fibers. Only the polyamide (wool) portion can be dyed or also the polyamide portion can be dyed according to the invention and the polyester portion can be dyed simultaneously with dispersion dyestuffs.

The fibers are impregnated by conventional techniques, e.g. by printing, coating or spraying, preferably however, by padding (foularding). Impregnation solutions according to the invention are advantageuosly produced by mixof a soluble salt of saturated aliphatic monocarboxylic acid having 8 to 14 carbon atoms and 5 to 30 g.'/liter of a polyglycol ether of fatty alcohols or fatty acids having 8 to 14 carbon atoms, which polyglycol ethers contain 4 to 12 ether groups and optionally other auxiliaries and preferably an amide of saturated, aliphatic monocarboxylic acids having 8 to 14 carbon atoms; the liquor has the above-mentioned pH range, or is adjusted to the same in the usual manner. The polyamide fibers are impregnated advantageously at 4070 C. and then wrung out to the desired content of impregnation liquor which is about 40 to 110% of the weight of the fibers, and preferably at least 80% in the case of wool.

When the impregnated polyamide fibers are steamed this is done by the usual methods, advantageously with neutral saturated steam. Wool and silk are steamed at about 90-120 C; synthetic fibers are steamed at 90-140" 0.; the preferred temperature range for steaming under substantially ambient pressure is at about 101 to 130 C.

The fixing of the dyestuff of the polyamide fibers by 7 treatment in a hot acid bath is performed by the known methods. Advantageously the content of acid for this purpose is about 5 to 15 g./ liter. The goods are introduced into the acid bath advantageously at -98 C. Inorganic and organic acids are suitable for the acid bath. Examples 1 of suitable inorganic acids are sulfuric acid, phosphoric acid or hydrochloric acid and examples of suitable organic acids are formic acid or acetic acid. Organic acids are preferred, in particular formic acid. In some cases it is useful to also add to the acid bath water-soluble salts, preferably water-soluble calcium salts of mineral acids, in particular calcium chloride.

The goods treated by acid shock or by steaming are rinsed with cold or Warm water which can contain the auxiliaries usual in the dyeing industry, e.g., formic acid oracetic acid, or also wetting or wash-active substances.

Compared with similar known processes, the process for the dyeing of polyamide fibers according to the invention has the following advantages: the impregnation liquor is homogeneous and substantially insensitive to electro lytes; it is thus more stable in the continuous process; in addition, even when producing very deep shades, a more level dyeing is obtained; it is also possible to dye blended wool material of various origin and quality and nevertheless obtain the same good level dyeing as with wool of a single source and quality, particularly when the dyebath contains the above-described amides of saturated aliphatic monocarboxylic acids as adjuvant besides the decisive homogeneity-maintaining mixture of water-soluble salt (a) and polyglycolethers (b). The fibers dyed according to the invention retain a soft feel and can be spun better; also the impregnation liquors are easily produced, they have, so to speak, unlimited stability and they do not substantially soil the apparatus; finally, a previous drying of the impregnated goods can be avoided which is a saving in time and apparatus.

In a second aspect, this invention concerns a process for producing prints on woollen goods, particularly on non-chlorinated woollen woven fabrics and yarns, by fabric printing methods; it further relates to the printing pastes used for this purpose as well as, as industrial product, the woollen fabrics and yarns so printed.

It is known that sufficiently vivid woollen prints of the necessary color strength can only be attained on chlorinated woollen woven fabrics or yarns. This naturally necessitates a pre-treatment of the woollen goods to be printed with chlorine-containing liquor, especially aqueous sodium hypochlorite solution which, apart from the additional work involved, also has the disadvantage that it injures the wool fibers. Another disadvantage of the known .process is that chlorinated woollen fabrics and yarns by fabric-printing methods, give only uneven and dull prints which in no way meet the present day requirements of the printing industry. Therefore, the printing of unchlorinated wool has only been applied in vigoureux printing, usually of black and grey shades on woollen slubbing which is ,used,'for instance, in the manufacture of fil-a-fil gents and ladies apparel in cases where dyed prints are not odjectionable.

It is, therefore, an object of this aspect of the invention to provide a process which'permits obtainment of strong prints on unchlorinated wool fabric, whereby the disadvantages connected with the known chlorination of the woollen fabrics and yarns prior to printing are avoided. The prints produced on unchlorinated wool by this process according to the invention are just as good as those attained on chlorinated wool.

The process according to this aspect of the invention consists in printing unchlorinated woollen fabrics or yarns at room temperature and a pH of at least 2, with a printing paste which contains at least one acid wool dyestulf, which paste contains as carriersoluble salts of saturated, aliphatic monocarboxylic acids having 8 to 14 carbon atoms as well as polyglycol ethers of fatty alcohols or fatty acids having 8 to 14 carbon atoms, which polyglycol ethers have 4 to 12 ether groups, and, optionally, other auxiliaries, and fixing the printed goods by steaming with subsequent rinsing.

By fabric printing as used in describing this aspect of the invention, there is meant only the textile printing of fabrics or yarn, and not the vigoureux printing methods mentioned hereinbefore.

The above-mentioned fixing treatment of the freshly printed-on Woollen fabric or yarn involves drying the said material at a temperature not exceeding 70 C., preferably of about 40 to 60 C., and then steaming the material with saturated steam of about 101-102 C. in a conventional steaming apparatus.

The steamed, printed material is then rinsed in cold water and may then either be allowed to dry or may be subjected to other conventional finishing treatments, such as soaping and the like.

As salts of saturated aliphatic carboxylic acids, the printing paste used according to the invention contains, for example, alkali metal salts such as lithium, sodium or potassium salts, or also ammonium salts of caprylic, pelargonic, capric, lauric or myristic acid or the salts of the mixture of acids comprised in the term coconut oil fatty acids, or of decyloxy, lauryloxy, decylmercapto or laurlymercapto acetic acid. In ammonium salts, the ammonium ions can contain N-substituents, particularly alkyl groups having 1 to 4 carbon atoms which alkyl groups may be substituted by the hydroxyl group or by a lower alkoxy group, preferably of 1 to 2 carbon atoms.

Particularly, polyglycol ethers having 5 to ether groups are useful in the fabric printing pastes according to the invention. These polyglycol ethers are the reaction products of fatty alcohols or fatty acids, having 8 to 14 carbon atoms, with from 5 to 10 equivalents of ethylene oxide; preferably, lauryl alcohol is used as fatty alcohol, and as fatty acids there are used those mentioned above in the discussion of the carboxylic acid salts, in particular the coconut oil fatty acids.

Advantageously, the weight ratio of the fatty acid salts as defined to the polyglycol ethers in the paste is about 1:1.

Particularly beautiful prints are obtained with a printing paste which also contains amides obtained by reaction of saturated, aliphatic monocarboxylic acids having 8 to 14 carbon atoms with ammonia or primary or secondary amines which contain at least one hydroxylower alkyl group. Such amides are derived, for example, from the fatty acids mentioned above in the discussion of the salts of fatty acids and from ammonia or the following aliphatic amines:

(a) mono-(hydroxy-lower alkyl)-amine such as ,B- hydroxyethylamine, 'y hydroxypropylamine or fi,'ydihydroxypropylamine,

(b) bis-(hydroxy-lower alkyl)-amine such as bis-(B- hydroxyethyD-amine, bis-('y-hydroxypropyD-amine 0r bisa-methyl-fi-hydroxyethyl -amine,

(c) N-alkyl-N-(hydroxy-lower alkyl)-amines such as N- methylor N-ethyl-N-(B-hydroxyethyl)-amino, or N- methylor N-ethyl-N-(hydroxy-propyl)-amine.

The bis-(hydroxyalkyl)-amides of the fatty acids described above, particularly of the coconut oil fatty acids, are preferred, and especially those amides the hydroxyalkyl radicals of which have from 2 to 3 carbon atoms, because they give a particularly good color yield.

These amides are obtained by reacting esters of suitable fatty acids with lower alkanols, e.g. fatty acid methyl or ethyl ester, with the desired amine, the reaction being performed in the presence of sodium or potassium alcoholate.

The printing paste to be used according to this aspect of the invention contains, as carrier, the fatty acid salts and polyglycol ethers as defined under the first aspect of the invention, as well as, optionally, the amides mentioned above, preferably in amounts of, in all, about to 40 grams, preferably in amounts of about 30 grams per kilogram of paste. In addition, it contains thickeners in amounts conventional in the fabric printing industry, in particular soluble types of gum such as so-called crystal-gum, or thickeners having a cellulose basis such as carob bean flour, tragacanth, galactomaunan, British gum, orin alkaline mediumalso the watersoluble salts of alginic acids, or cellulose derivatives such as methyl cellulose or soluble salts of carboxymethyl cellulose. As further auxiliaries, the paste can also contain acids, in particular lower fatty acids such as formic acid and, mainly acetic acid, organic solvents such as alcohols, particularly lower alkanols such as isopropanol, glycols such as ethylene glycol or thiodiethylene glycol, or triols such as glycerin, as well as carbonic acid amides and thiocarbonic acid amides, in particular urea or thiourea.

The acid wool dyestuffs in the printing paste usable according to this aspect of the invention can be of the most various classes of dyestuffs. Preferably they are of the technically proved classes of azo, anthraquinone, phthalocyanine, nitro or formazane dyestuffs which, if desired, may also contain metals such as copper, nickel, chromium or cobalt. As azo dyestuffs mainly monoazo dyestuffs are used, e.g. those of the type benzene-azohydroxybenzene, benzene azo aminobenzene, benzeneazo-hydroxynaphthalene, benzene-azo-aminonaphthalene, benzene azo hydroxypyrazole, 'benzene-azo-aminopyrazole, benzene-azo-acyloacetylarylamide or those of the analogous naphthalene-azoand heterocycle-azo types, whereby as heterocycles, five or six-membered heterocycles, particularly those containing nitrogen, can be mentioned such as thiazoles, imidazoles, triazoles, oxdiazoles, thiadiazoles, pyrimidines, benzothiazoles, 'benzotriazoles, indazoles, quinolines. However, also polyazo dyestuffs can be used. The azo dyestuffs can be metallized, principally by chromium or cobalt, but also by copper or nickel. Particularly favorable results are produced by heavy-metal containing azo dyestuffs, i.e. chromium or cobalt containing azo dyestuffs, preferably monoazo dyestuffs which contain one metal atom bound to two molecules of dyestutf.

The woollen fabrics and yarns to be printed according to this aspect of the invention can be of pure wool or mixed fabrics, in the latter case preferably a blended fabric of wool and polyester fibers. By polyester is meant high molecular organic esters such as cellulose dito tri-acetate, particularly, however, polymeric esters of aromatic polycarboxylic acids with polyvalent alcohols, especially polyglycol terephthalate. It is possible to print only the wool part or also both the wool and polyester parts together.

The woollen fabric or yarn is printed and the printed goods are steamed by conventional methods. Beautiful, strongly colored prints are obtained.

The printed goods are advantageously rinsed, for example, with cold or warm water which can contain the auxiliaries usual in textile printing, e.g. formic acid or acetic acid, or, wetting agents or detergents.

The following non-limitative examples serve to illustrate the invention further. The temperatures given therein are in degrees centigrade. Where not otherwise stated, parts and percentages are given by weight. The relationship of parts by weight to parts by volume is as that of grams (g.) to milliliters (ml.). (3.1. means Color Index, second edition, 1956, published by the Society of Dyers and Colourists, Bradford, England, and The American Association of Textile Chemists and Colorists, Lowell, Mass, U.S.A.

Example 1 40 parts of the commercial form of the chromium complex compound of the monoazo dyestulf Z-aminophenol- 4-methylsulfone- 1-phenyl-3-methyl pyrazolone (molar ratio of dyestuffzchromium is 2:l)-containing about 50% of dextrin as diluting agent '(coupage)-are dissolved in 60-warm mixture of 300 parts of an aqueous 2.5% solution of carob bean flour and 30 parts of a carrier mixture consisting of bis-(fi-hydroxyethyD-amine salt of coconut oil fatty acids and the condensation product of 1 mol of dodecyl alcohol and 5 mols of ethylene oxide in a weight ratio of 1:1, which 30 parts have been admixed with 250 parts of water. The resulting solution is diluted to 900 parts with warm water (70 C.), and the pH is adjusted to about 6 with dilute acetic acid. The temperature of the mixture should then be about 60. Wool flannel is impregnated at 60 with this, liquor, squeezed out to a liquor content of about 80% calculated on the dry weight of the goods and steamed with saturated steam at 102 under slight excess pressure for 4 minutes. The goods are then washed with a solution containing 1 g./liter of nonylphenol polyglycol ether, then rinsed with water, then washed with an aqueous solution containing 2 mL/liter of 85%-formic acid and, if necessary, again rinsed with water. A level and well-penetrated orange Wool dyeing is obtained which has no so-called sandwich effect.

If the steaming time in the above example is varied to 8, 15, 30 or 60 minutes, then in each case a weaker or deeper but otherwise equivalent orange wool dyeing is obtained.

By using, in the above example, instead of the dyestuff mentioned, similar chromium-containing monoazo dyestuffs of the type containing 2 dyestufl molecules per chromium atom (2:1 complexes) which contain no sulfonic acid groups but which are substituted by lower alkyl-sulfonyl groups or which contain sulfonic acid amide groups which may be substituted at the nitrogen atom by alkyl groups, for example, the chromium-containing dyestufi:Z-aminophenol-S-sulfonic acid amide- 1-phenyl-3- methyl-pyrazolone; the chromium-containing dyestuir' mixture:2-amino-5-nitrophenol 2 hydroxynaphthalene, 2-amino-5-nitrophenoll-hydroxynaphthalene 3,6 bissulfonic acid methylamide (dyestuif:chomium=2:l); or the chromium-containing monoazo dyestuffzZ-aminophenol-4-methylsulfone l-acetylamino-7-hydroxy naphthalene (dyestufl:chromium=2.l), while otherwise the procedure given in the above example is followed; equally well penetrated and level red, navy blue or grey colored wool flannel dyeings, respectively, are obtained.

By using, instead of the carrier mixture given in the above Example 1, the same amount of a mixture which consists of: 1 part of the sodium or potassium salt of coconut oil fatty acids and 1 part of the condensation product of 1 mol of decyl alcohol and 6 mols of ethylene oxide or 1 part of N-methyl-N-(B-hydroxyethyl)-amine salt of lauric or myristic acid and 1 part of the condensation product of 1 mol of tetradecyl alcohol and 6 mols of ethylene oxide, and otherwise following the procedure given in the example, paragraph one, equally well penetrated and level dyeings are obtained.

Similarly good results are obtained when using, in the above example, instead of carob bean flour solution, an identical amount of aqueous sodium alginate solution.

Example 2 Wool flannel is impregnated at 60 with an impregnation liquor produced according to Example 1, first paragraph, and wrung out to a liquorcontent of about 80%. The foularded fabric is passed through a 98-hot aqueous bath which contains 8 ml./liter of aqueous 85%-formic acid at a. rate allowing the material to be in the bath for 5 minutes. Only a negligible bleeding of the dyestuff into the bath occurs. The wool flannel so dyed is then washed for 5 minutes with a 45 warm aqueous solution of 0.5 g./liter of nonylphenol polyglycol ether and then rinsed with cold water. The orange dyeing obtained is well penetrated and has no so-called sandwic effect.

By using, instead of the carrier mixture given in Example 1, first paragraph, the same amount of a mixture consisting of, in a weight ratio of 1:1, tri-(p-hydroxyethyl)-amine salts of coconut oil fatty acids, bis-'(p-hydroxyethyl)-amine salts of coconut oil fatty acids, dimethylamine salts of coconut oil fatty acids, or the mor pholine salt of coconut oil fatty acids or N-methyl-N,N- bis-(fi-hydroxyethyD-amine salt of coconut oil fatty acids, bis-(fl-hydroxyethyD-amine salt of lauric acid, bis-(fihydroxyethyl)-amine salt of pelargonic acid, ethylamine salt of coconut oil fatty acids or the sodium or potassium salt of coconut oil fatty acid with, in each case, the condensation product of 1 mol of dodecyl alcohol and 5 mols of ethylene oxide is used and otherwise the procedure described in the example is followed, then equally Well penetrated and level dyeings are obtained.

Example 3 W001 flannel is impregnated in the foulard at 40 with a liquor which, instead of the metal-containing azo dyestuif mentioned in paragraph 1 of Example 1, contains the dyestuif Polar Brilliant Blue GAW (C.I. 61,135, Acid Blue 127), but which is otherwise produced according to paragraph 1 of Example 1, and wrung out to a liquor content of The goods are then steamed for 4 minutes at 102 under slight excess pressure. The goods are then Washed with a solution containing 1 g./ liter of nonylphenol polyglycol ether, then rinsed with water, washed with an aqueous solution containing 2 mL/Iiter of formic acid and, if necessary, again rinsed with water.

A level and well penetrated blue wool dyeing is obtained which has no so-called sandwich effect.

If instead of Polar BrilliantBlue GAW, the disazo dyestufr coupled in acid medium of the formula NHz Hogsor the dyestufl Neolan Yellow 8GE (C.I. Acid Yellow 101) containing 1 chromium atomzl dyestuff molecule is used and otherwise the procedure described in the example is followed, then equally good and level red or yellow material which is well penetrated is obtained.

. Example 4 40 parts of the disazo dyestuff Woolen slubbing is impregnated at 60 with this solution, the pH of which has been adjusted to 6 with acetic acid, wrung out to a liquor content of about 80% and steamed for 30 minutes at 98 under slight excess pressure. The goods are then rinsed with a 50 warm aqueous solution of 0.5 g./liter of a condensation product according to U.S.P. 2,089,212, then rinsed with water at about 30, then treated with a 30 warm aqueous solution of 0.2 ml./liter of 85% formic acid and finally rinsed again with 30 warm water.

Woollen slubbing which is evenly dyed red is obtained. It can be well combed and spun.

Example 5 80 parts of Eriochrome Black A (C.I. 15,710) are dissolved in a 60 warm mixture of 300 parts of a 2.5% sodium alginate solution and 30 parts of a mixture consisting, in a weight ratio of 1:1, of N-methyl-N-(p-hydroxyethyl)-amine salt of coconut oil fatty acid and of the condensation product of 1 mol of coconut oil fatty acids and 5 mols of ethylene oxide, as well as parts of potassium chromate, both said mixture and potassium chromate being dissolved in 250 parts of warm water. The solution obtained is diluted with water to 1000 parts; the temperature should be 20.

Woollen slubbing is impregnated with this liquor at 20-30", wrung out to a liquor content of about 100% and steamed with saturated steam for 1 hour at 98. The goods are then rinsed with an aqueous solution of 0.5 g./liter of a condensation product according to U.S.P. 2,089,212 in a back-washing machine, rinsed with water at about 30, then acidified in a new bath with an aqueous 30 warm solution of 0.2 ml./liter of 85% formic acid and finally again rinsed with 30 warm water.

Woollen slubbing dyed a level black is obtained. It can be well combed and spun.

Example 6 45 parts of Eriochrome Red B (C.I. 18,760), 27.5 parts of Eriochrome Brilliant Red BL (Cl. 17,995) and 0.9 part of Eriochrome Blue SE (C.I. 16,680) are dissolved in a 60 warm mixture of 300 parts of a 2.5 aqueous sodium alginate solution and 30 parts of a mixture of, in a weight ratio of 1:1, N-methyl-N-(fl-hydroxyethyD-amine salt of coconut oil fatty acid and the condensation product of 1 mol of tetradecyl alcohol and 7 mols of ethylene oxide, as well as 10 parts of sodium chromate, in mixture with 250 parts of warm water. The solution obtained is diluted with warm water to 1000 parts. The temperature should be 60.

Woollen slubbing is impregnated with this liquor at 60, wrung out to a liquor content of about 80% and steamed for 30 minutes at 98 with saturated steam. The goods are then rinsed with a 50 warm aqueous solution of 0.5 g./liter of a condensation product according to U.S.P. 2,089,212, rinsed with water at about 30, then treated with a 30 warm aqueous solution of 0.2 ml./ liter of 85 formic acid and finally again rinsed with 30 warm water.

Level, red, penetrated woolen slubbing is obtained which can be well combed and spun.

If in the above example instead of the dyestufis given, a mixture is used consisting of 28 g./liter of Eriochrome Cyanine R (C.I. 42,571) and 0.9 g./liter of Eriochrome Blue SE (C.I. 16,680) and otherwise the procedure given in the example is followed, then an equally well dyed and penetrated blue woolen slubbing dyeing is obtained.

Example 7 Silk serge is impregnated at 40 with an impregnation liquor produced according to Example 1 paragraph 1, wrung out to a liquor content of 80% and treated for 5 minutes in a 98 warm aqueous bath which contains 8 ml./liter of formic acid. Only a very slight bleeding of the dyestulf into the acid bath occurs. The goods are afterwards washed with a 45 warm aqueous solution of 0.5 g./1iter of nonylphenol polyglycol ether and then rinsed with cold water.

In this way, well penetrated orange silk serge of good evenness is obtained which has no so-called sandwich effect.

Corresponding yellow dyeings on silk serge with equally good penetration of the material and evenness of the dyeings are obtained, if instead of the dyestutf mentioned in the above example, the dyestuif Neolan Yellow SGE (C.I. Acid Yellow 101) is used and otherwise the procedure given in the example is followed.

Example 8 37.5 parts of the chromium-containing monoazo dyestuff: 2 carboxy-l-aminobenzene I-phenyI-B-methylpyrazolone (dyestutf: chromium=2z1), and 14.0 parts of the chromium-containing monoazo dyestuff: 2-aminophenol 4 sulphonic acid methylamide l-carboethoxyamino-7-hydroxynaphthalene (dyestulf: chromium=2zl) are dissolved in an 80 warm mixture containing 300 parts of a 2.5 aqueous sodium alginate solution and 10 parts of a mixture, in a weight ratio of 1:1, of N-methyl-N-(fihydroxyethyl)-amine salt of coconut oil fatty acid with the condensation product of 1 mol of dodecyl alcohol and 7 mols of ethylene oxide, which 10 parts are admixed with 290 parts of water, and the solution obtained is diluted with cold water to 1000 parts. The temperature is then about 40.

Nylon canvas is impregnated with this liquor, wrung out to a liquor content of 50% of the weight of the fibers, steamed for 8 minutes at a temperature of and then rinsed first with hot and then with cold water.

An olive, well penetrated nylon canvas is obtained and the dyeing is very level.

Example 9 Nylon canvas is impregnated at 40 with an impregnation liquor produced according to Example 8 paragraph 1 but which only contains 36 of the amount of dyestuif given in that example. The goods are then wrung out to a liquor content of 50% of the weight of the fibres and then treated for 4 minutes in a 98 warm aqueous both containing 4 ml./liter of 85 formic acid. Only an inconsiderable bleeding of the dyestuif into the acid bath occurs. The nylon canvas so dyed is then rinsed with warm and cold water; a good and level olive dyeing is obtained.

Example 10 A poly-e-aminocaprolactam (Perlon, Perlon-Warenzeichenverband, Registered Company, Frankfurt Company, Frankfurt am Main, Germany) is impregnated at 40 with a liquor produced according to Example 9), wrung out to a liquor content of 50% of the weight of the fibres and dried under thermo-fix conditions for 45 seconds at 190.

The Perlon canvas so impregnated is entered into a 98 warm aqueous bath which contains 4 ml./liter of 85% formic acid and treated in this bath for 4 minutes at the boil. It is then rinsed first with warm and then with cold water.

An evenly penetrated olive Perlon canvas is obtained.

Example 11 2.5 parts of the cobalt-containing monoazo dyestufi: 2- aminophenol-4-sulphonic acid methylamide- 1-phenyl-3- methyl-pyrazolone (dyestuif:cobalt=2:1) and 0.5 part of the chromium containing monoazo dyestulf: 2-amino-4- nitrophenol 1-phenyl 3 methyl-pyrazolone (dyestuff: chromium=2: l) are dissolved in an 80 warm mixture of 300 parts of a 2.5% aqueous sodium aliginate solution and 30 parts of a mixture of, in a weight ratio of 1:1,

N-methyl-N-(fl-hydroxyethyD-amine salt of coconut oil' fatty acid with the condensation product of 1 mol of dodecyl alcohol and 5 mols of ethylene oxide. The solution obtained is diluted with suflicient cold water to make 1000 parts by volume. Woolen slubbing is impregnated at 40 with this liquor, the pH of which has been adjusted to 6 by the addition of acetic acid, wrung out to a liquor content of 103% calculated on the fibres, and then steamed for 8 /2 minutes at 104 with saturated steam.

The goods are then washed with a solution containing 1 g./litre of nonyl phenol polyglycol ether and 1 mL/liter of concentrated ammonia solution, then rinsed with Water, then washed with an aqueous solution containing 2 ml./ liter of 85% formic acid and, if necessary, again rinsed with water.

The orange-red woolen slubbing so dyed is well penetrated and is very level. The feel of the goods is soft and voluminous and the material can be well combed and spun.

Example 12 Woolen slubbing is printed in the known manner of vigoureux printing with a solution produced according to Example 1 paragraph 1 but which contains 500 parts instead of 300 parts of sodium aliginate solution and instead of the dyestulf given in that example, 40 parts of the chromium-containing monoazo dyestutf Z-aminophenol-4-sulfonic acid ethylamide l-acetylamino-7-hydroxynaphthalene (dyestuif:chromium=2: 1). The takeup of liquor is about 60% The goods are after-treated by steaming and rinsing as described in Example 1.

Grey coloured woolen slubbing is obtained which is distinguished by a full voluminous feel. The goods can be combed and spun well.

Example 13 40 parts of the chromium-containing monazo dye-stuff 2-aminophenol-4-methylsulfone 1 acetylamino 7-hydroxynaphthalene (dyestutf:chromium=2: 1) are dissolved in a 60 warm mixture of 300 parts of -a 2.5% aqueous sodium alginate solution and 15 parts of N- methyl-N- (B-hydroxyethyD-amine sailt of coconut oil fatty acid, 15 parts of the condensation product of 1 mol of tetradecyl alcohol and 6 mols of ethylene oxide, and 15 parts of coconut fatty acid N,N-bis- B-hydroxyethyl)- amide, mixed with 250 parts of water. The solution obtained is made up of 1000 parts with water. The temperature of the solution should be 60.

Wool flannel is impregnated at 60 with this liquor, and wrung out to a liquor content of 80%. The foularded fabric is entered into a 98 warm aqueous bath which contains 8 ml./liter of 85 formic acid and is treated in this bath for 5 minutes.

The grey wool flannel dyed in this way is washed with a 45 warm aqueous solution of 0.5 g./liter of nonylphenol polyglycol ether and then rinsed with cold water. In this way a well penetrated grey wool flannel is obtained which has good evenness and is without a so-called sandwic efi'ect.

If in the above example instead of the dyestuff mentioned the cobalt-containing monazo dyestuif 2-amino-4- chlorophenol 2 hydroxynaphthalene 6 sulphonic acid methylamide (dyestuff:cobalt=2: 1) or the chromium-containing monoazo dyestuif 2-amino 4 chlorophenol-+1 hydroxynaphtalene 3 sulphonic acid amide (dyestuff:chromium=2:1) is used and otherwise the procedure given in the example is followed, then Wool flannel dyed ruby red or blue respectively is obtained. The dyeings are equally level and well penetrated.

Similarly good dyeings are obtained if, instead of the N methyl N (ii-hydroxyethyl) amine salt mentioned in the example, the methylamine salt, morpholine salt, tri (B hydroxyethyl) amine salt, bis-(a-methyl B- hydroxyethyl)-amine salt, sodium salt or potassium salt 14 of coconut oil fatty acid or the B-hydroxyethyl-amine salt of lauric acid is used in each case with the condensation product mentioned in the example.

Example 14 Woollen slubbing is foularded at 60 with an impregnation liquor produced according to paragraph 1 of Example 13 but containing the dyestutt Polar Brilliant Blue GAW (C.I. 61,135, Acid Blue 127) instead of the metalcontaining azo dyestuif mentioned in paragraph 1 of example 13, and the wrung out to a liquor content of about The goods are then entered into a 98 warm aqueous bath containing 8 ml./liter of formic acid. The goods are treated in this bath for 5 minutes.

Only an inconsiderable bleeding of the dyestulf into the acid bath occurs. The goods are then washed in a. back-washing machine with a 50 warm aqueous solution of 0.5 g./litre of nonylphenol polyglycol ether, rinsed with water at 30, treated in a new bath with an aqueous solution of 1.5 mL/Iiter of 85% formic acid and then rinsed with 30 warm water.

The blue woollen slubbing so dyed is well penetrated and can be Well combed and spun.

If instead of Polar Brilliant Blue GAW the dyestuffs mentioned in Example 3, paragraph 3 are used, then equally good and evenly penetrated woollen slubbing dyed red or yellow is obtained.

Example 15 Woollen worsted fabric is impregnated at 60 with an impregnation liquor produced according to Example 6, fourth paragraph and the goods are wrung out to a liquor content of 80%. The foularded fabric is then entered into a 98 warm aqueous bath containing 8 mL/liter of 85 formic acid. The fabric is treated in this bath for 5 minutes. An insignificant bleeding of the dyestuff into the acid bath occurs. The goods are then washed with a 45 warm aqueous solution of 0.5 g./litre of nonylphenol polyglycol ether and then rinsed with cold water.

The woollen worsted so obtained is well penetrated and the blue dyeings are very level without any so-called sandwic effect.

Example 16 40 parts of the dyestulf Eriochrome Blue SE (Cl. 16-,- 680) are dissolved in a 60 warm mixture of 300 parts of a 2.5% aqueous sodium aliginate solution, to which are added 15 parts of N-methy1-N-( fi-hydroxyethyl)- amine salt of coconut oil fatty acid and 15 parts of the condensation product of 1 mol of dodecyl alcohol and 5 mols of ethylene oxide as well as 10 parts of potassium chromate in 250 parts of water. The solution obtained is made up to 1000 parts with water and the pH is adjusted to 6 with acetic acid. The temperature should be 60.

Wool flannel is impregnated with this liquor at 60 and wrung out to a liquor content of 80%. The foularded fabric is entered into a 98 warm aqueous bath which contains 8 ml./liter of 85% formic acid and treated in this bath for 5 minutes. Only an inconsiderable bleeding of the dyestutf into the acid bath occurs. The blue wool flannel so dyed is then washed with a 45 warm aqueous solution of 0.5 g./litre of nonylphenol polyglycol ether and then rinsed with cold water. In this way a well penetrated very even blue wool flannel is obtained which has no so-called sandwich effect.

If in the above example instead of the dyestuff mentioned, Eriochrome Yellow C (C.I. 25,100) or Eriochrome Red G (C.I. 18,750) is used then corresponding yellow or red coloured wool flannel is obtained. The dyeing has equally good penetration and evenness.

Example 17 Wool flannel is impregnated and steamed according to Example 1. The goods, while still moist, are entered into a 98 warm aqueous bath which contains 8 ml./liter of 85% formic acid and are kept in this bath for minutes, only an inconsiderable bleeding of the dyestuff occurring. The wool flannel so dyed is then washed in a 45 warm aqueous solution of 0.5 g./liter of nonylphenol polyglycol ether and afterwards rinsed with cold water.

Well penetrated, very level orange wool flannel is obtained which has no sandwich effect.

Example 18 A fabric consisting of 45 parts of wool and 55 parts of Terylene (I.C.I. Manchester, England) is impregnated and steamed analogously to Example 1. The wool portion of the fabric is dyed orange whilst the polyester portion remains substantially undyed.

Example 19 A mixed fabric of wool and cellulose triacetate is impregnated and steamed analogously to Example 1. The wool part of the fabric is dyed orange whilst the triacetate part remains substantially undyed.

Example 20 Wool flannel is impregnated in the foulard at 40 with a liquor which, instead of the metal-containing azo dyestuif mentioned in paragraph 1 of Example 1, contains the dyestutf Polar Brilliant Red B (Cl. 17,995, Acid Red 133), but which is otherwise produced according to paragraph 1 of Example 1, and wrung out to a liquor content of 100%. The goods are then steamed for 15 minutes at about 95 to 98 C. The goods are then washed with a solution containing 1 g./liter of nonylphenol polyglycol ether, then rinsed with water, washed with an aqueous solution containing 2 ml./1iter of 85% formic acid and, if necessary, again rinsed with water.

A level and well penetrated red wool dyeing is obtained which has no so-called sandwich effect.

If, instead of Polar Brilliant Red B, the dyestulf coupled in acid medium of the formula NH: NH:

or the dyestuff Neolan Yellow 8GB (C.I. Acid Yellow 101) containing 1 chromium atomzl dyestutf molecule is used and otherwise the procedure described in the example is followed, then equally good and leve lred or yellow material which is well penetrated is obtained.

Example 21 Woollen slubbing is foularded at 60 with an impregnation liquor produced according to paragraph 1 of Example 13 but containing the dyestuff Polar Brilliant Red B (C.I. 17,995, Acid Red 133) instead of the metalcontaining azo dyestutf mentioned in paragraph 1 of Example 13, and then wrung out to a liquor content of about 100%. The goods are then entered into a 98 warm aqueous bath containing 8 ml./liter of 85% formic acid. The goods are treated in this bath for 5 minutes.

Only a momentary bleeding of the dyestuff into the acid bath occurs and this ceases immediately. The goods are then washed in a back-washing machine with a 50 warm aqueous solution of 0.5 g./liter of nonylphenol polyglycol ether, rinsed with water at 30", treated in a 16 new bath with an aqueous solution of 1.5 .ml./liter of 85% formic acid and then rinsed with 30 warm water.

The red woollen slubbing so dyed is well penetrated and can be well combed and spun.

If, instead of Polar Brilliant Red B, the dyestulfs mentioned in Example 3, paragraph 3, are used, then equally good and evenly penetrated woollen slubbing dyed red or yellow is obtained.

Example 22 20 g. of the dyestuif C.I. Acid 85 (No. 22,245) are mixed with 60 g. of urea and the mixture is pasted with 50 ml. of cold water. 330 ml. of boiling water are poured over the paste and 50 g. of thidiethylene glycol, 400g. of aqueous %-acetic acid and 30 g. of-

(a) A mixture of 35 parts of the N-methyl-N,N-bis- (fl-hydroxyethyD-amine salt of coconut oil fatty acids, 35 parts of lauryl alcohol pentaglycol ether and 30 parts of N,N-bis-(/3-hydroxyethyl)-amide of coconut oil fatty acid are admixed therewith in a conventional blender. The mixture is made up to 1000 g. with water.

Closely woven woollen fabric is printed by a conventional fabric printing method with the above paste, dried in a drying chamber at about 50, and then steamed with saturated steam of 101-102" and rinsed with cold water. Vivid, brilliant, scarlet prints are obtained.

Prints having similar properties are obtained if, with otherwise the same procedure, instead of the 30 g. of the mixture (a) of amine salt, polyglycol ether and amide given in the example, the same amounts of the following mixtures are used:

(b) 35 parts of bis-(fl-hydroxyethylamine) salt of coconut oil fatty acids, 30 parts of lauryl alcohol pentaglycol ether, and 30 parts of N,N-bis-(' -hydroxypropyl)- amide of coconut oil fatty acid;

(c) 40 parts of the sodium or potassium salt of coconut oil fatty acids, 35 parts of lauryl alcohol decaglycol ether, and 30 parts of lauric acid-N,N-bis-(p-hydroxyethyl)-amide;

(d) 1 part of bis-(,S-hydroxyethyl)-amine salt of coconut oil fatty acids, and 1 part of the condensation product of 1 mol of dodecyl alcohol and 5 mols of ethylene oxide;

(e) 1 part of the sodium salt of coconut oil fatty acids, and 1 part of the condensation product of 1 mol of decyl alcohol and 6 mols of ethylene oxide;

(f) 1 part of N-methyl-N-(fi-hydroxyethyl)-amine salt of lauric or myristic acid, and 1 part of the condensation product of 1 mol of tetradecyl alcohol and 6 mols of ethylene oxide;

(g) 35 parts of N-methyl-N,N-bis-(,8,'y-dihydroxypropyl)-amine salt of coconut oil fatty acid, 35 parts of myristyl alcohol pentaglycol ether and 30 parts of N,N- bis-(fl-hydroxyethyD-amide of coconut oil fatty acid,

(h) 35 parts of tri (B hydroxyethyl)-amine salt of coconut oil fatty acids, 35 parts of lauryl alcohol pentaglycol ether and 30 parts of N,N-bis-(fl-hydroxyethyD- amide of coconut oil fatty acid,

(i) 35 parts of dimethylamine salt of coconut oil fatty acids, 35 parts of lauryl alcohol pentaglycol ether and 30 parts of N,N-bis-(fl-hydroxyethyD-amide of coconut oil fatty acid,

(j) 35 parts of morpholine salt of coconut oil fatty acids, 35 parts of lauryl alcohol pentaglycol ether and 30 parts of myristic acid-N,N-bis-(fi-hydroxyethyD-amide,

(k) 35 parts of ethylamine salt of coconut oil fatty acids, 35 parts of lauryl alcohol pentaglycol ether and 30 parts of N,N-bis-(fl-hydroxyethyD-amide of coconut oil fatty acid.

If in the above example, with otherwise the same procedure instead of the dyestufi mentioned in the example, the same amounts of the dyestuffs given in column II of the following Table I are used, then prints having similar properties are obtained which are of the shades given in column III of the table.

TABLE I III- shade on II-dyestufi Wool 23 C.I. Acid Blue 126 Blue.

24 Green.

SOrNHz I S02 l O\ IL Cr(|) ll 00 N 3)\ Q 2-amino-4-nitrophen0l 4-methylphenol (2:1 chromium com lex) Brown.

26 NHz H21? Yellow.

l-phenyl-3-methyl-5-aminopyrazole-4-sulphonic acid 27 Mixture, consisting of: 75 parts of 1-amin0naphthalene5-sulphonic acid-l-amino- Black,

naphtha1ene-1-phenylaminonaphthalene-S-sul honic acid, 6 parts of 0.1. Acid Green 9 (No. 42,100), 3.38 parts of 0.1. Acid range 63, reduced with 15.62 parts of sodium sulphate.

We claim: at a temperature below the drawing temperature of the 1. In processes for the pad-dyeing, printing, coating and spraying of polyamide fibers, which processes comprise impregnating these fibers with a thickened aqueous liquor containing an acid wool dyestufi and a thickener, at a temperature below the drawing temperature of the dyestufi', whereby the dyestufi is deposited on the fibers without drawing on them substantively, and then heating the impregnated goods to at least 80 C. in a humid medium, and thereby fixing the dyestuff on the fiber, the improvement which comprises (a) adding to the impregnation liquor prior to the impregnation of the fiber therewith (1) as color transfer agent for transferring the said acid wool dyestuif during fixing from the deposit on the fiber into the interior of the fiber, an effective amount of a water-soluble salt of a saturated aliphatic monocarboxylic fatty acid having 8 to 14 carbon atoms with a monoto divalent cation selected from the group consisting of alkali metal ion, ammonium ion, lower alkyl-substituted ammonium ion, hydroxy-lower alkyl-substituted ammonium ion, lower 'alkoxyalkyl substituted ammonium ion, morpholinium ion, piperidinium ion, and hydroxy-(lower alkyl)-substituted ethylene-diammonium ion, and

(2) a polyglycolether selected from the group consisting of fatty alcohols and saturated fatty acids having 8 to 14 carbon atoms, each mole of which is condensed with 4 to 12 equivalents of ethylene oxide, and

(b) adjusting the pH of the impregnation liquor to at least 5 and higher.

2. In processes for the pad-dyeing, printing, coating and spraying of polyamide fibers, which processes comprise impregnating these fibers with a thickened aqueous liquor containing an acid wool dyestulf and a thickener dyestuff, whereby the dyestuff is deposited on the fibers without drawing on them substantively, and then steaming the impregnated goods in a humid medium, and thereby fixing the dyestufi on the fiber, the improvement which comprises (2.) adding to the impregnation liquor prior to the impregnation of the fiber therewith (1) as color transfer agent for transferring the said acid wool dyestufi" during steaming from the deposit on the fiber into the interior of the fiber, an effective amount of a water-soluble salt of a saturated aliphatic monocarboxylic acid having 8 to 14 carbon atoms with a monoto divalent cation selected from the group consisting of alkali metal ion, ammonium ion, lower alkyl-substituted ammonium ion, hydroxy-lower alkyl-substituted ammonium ion, lower alkoxyalkyl substituted ammonium ion, morpholinium ion, piperidinium ion, and hydroxy-(lower alkyl)-substituted ethylene-diammonium ion, and

(2) a polyglycolether selected from the group consisting of fatty alcohols and saturated fatty acids having 8 to 14 carbon atoms, each mole of which is condensed with 4 to 12 equivalents of ethylene oxide, and

(b) adjusting the pH of the impregnation liquor to at least 5 and higher.

3. In processes for the pad-dyeing, vigoureux printing, coating and spraying of polyamide fibers, which processes comprise impregnating these fibers with a thickened aqueous liquor containing an acid wool dyestuif and a thickener at a temperature below the drawing temperature of the dyestutf, whereby the dyestuff is deposited on the fibers without drawing on them substantively, and passing the impregnated goods through a hot acid shock bath, the improvement which comprises 19 (a) adding to the impregnation liquor prior to the impregnation of the fiber therewith (1) as color transfer agent for transferring the said acid wool dyestuif during the treatment in said acid shock bath from the deposit on the fiber into the interior of the fiber, an effective amount of a water-soluble salt of a saturated aliphatic monocarboxylic fatty acid having 8 to 14 carbon atoms with a monoto divalent cation selected from the group consisting of alkali metal ion, ammonium ion, lower alkylsubstituted ammonium ion, hydroxy-lower alkyl-substituted ammonium ion, lower alkoxyalkyl-substituted ammonium ion, morpholinium ion, piperidinium ion, and hydroxy-(lower alkyl)-substituted ethylene-diammonium ion,

and (2) a polyglycolether selected from the group consisting of fatty alcohols and saturated fatty acids having 8 to 14 carbon atoms, each mol of which is condensed with 4 to 12 equivalents of ethylene oxide, and

(b) adjusting the pH of the impregnation liquor to at least 5 and higher.

4. In processes for the pad-dyeing, vigoureux printing, coating and spraying of polyamide fibers, which processes comprise impregnating these fibers with a thickened aqueous liquor containing an acid wool dyestuff and a thickener at a temperature below the drawing temperature of the dyestutf, whereby the dyestuff is deposited on the fibers without drawing on them substantively, and then subsequently steaming the impregnated goods in a humid medium, and then passing the impregnated goods through a hot acid shock bath, the improvement which comprises (a) adding to the impregnation liquor prior to the impregnation of the fibers therewith (1) as color transfer agent for transferring the said acid wool dyestutf during fixing from the deposit on the fiber into the interior of the fiber, an effective amount of a water-soluble salt of a saturated aliphatic monocarboxylic fatty acid having 8 to 14 carbon atoms with a monoto divalent cation selected from the group consisting of alkali metal ion, ammonium ion, lower alkyl-substituted ammonium ion, hydroxylower alkyl-substituted ammonium ion, lower alkoxy-alkyl-substituted ammonium ion, morpholinium ion, piperidinium ion, and hydroxy- (lower alky1)-substituted ethylene diammonium ion, and

(2) a polyglycolether selected from the group consisting of fatty alcohols and saturated fatty acids having 8 to 14 carbon atoms, each mol of which is condensed with 4 to 12 equivalents of ethylene oxide, and

(b) adjusting the pH of the impregnation liquor to at least 5 and higher.

5. In processes for the pad-dyeing, printing, coating and spraying of polyamide fibers, which processes comprise impregnating these fibers with a thickened aqueous liquor containing an acid wool dyestuff and a thickener at a temperature below the drawing temperature of the dyestuff, whereby the dyestuif is deposited on the fibers without drawing on them substantively, and then heating the impregnated goods to 80 C. and higher in a humid medium, and thereby fixing the dyestuflf on the fiber, the improvement which comprises (a) adding to the impregnation liquor (1) as color transfer agent for transferring the said acid wool dyestutf during fixing from the deposit on the fiber into the interior of the fiber, an effective amount of water-soluble salt of a saturated aliphatic monocarboxylic fatty acid having 8 to 14 carbon atoms with a monoto divalent cation selected from the group consisting of alkali metal ion, ammonium ion, lower alkyl-substituted ammonium ion, hydroxylower alkyl-substituted ammonium ion, lower alkoxy-alkyl-substituted ammonium ion, morpholinium ion, piperidinium ion, and hydroxy- (lower alkyl)-substituted ethylene diammonium 1on,

(2) a polyglycolether selected from the group consisting of fatty alcohols and saturated fatty acids having 8 to 14 carbon atoms, each mol of which is condensed with 4 to 12 equivalents of ethylene oxide,

(b) adjusting the pH of the impregnation liquor to at least 5 and higher,

(c) impregnating said fibers with the resulting liquor,

and

(d) subsequently heating the impregnated goods in said humid medium directly without intermediate drying.

6. In processes for the pad-dyeing, printing, coating and spraying of polyamide fibers, which processes comprise impregnating these fibers with a thickened aqueous liquor containing an acid wool dyestuif and a thickener at a temperature below the drawing temperature of the dyestuff, whereby the dyestufi is deposited on the fibers without drawing on then substantively, and then heating the impregnated goods to at least C. in a humid medium, and thereby fixing the dyestutf on the fiber, the improvement which comprises (a) adding to the impregnation liquor prior to the impregnation of the fiber therewith (l) as color transfer agent for transferring the said acid wool dyestutf during fixing from the deposit on the fiber into the interior of the fiber, an effective amount of a water-soluble salt of a saturated aliphatic monocarboxylic fatty acid having 8 to 14 carbon atoms with a monoto divalent cation selected from the group consisting of alkali metal ion, ammonium ion, lower alkyl-substituted ammonium ion, hydroxy-lower alkyl-substituted ammonium ion, lower alkoxyalkyl-substituted ammonium ion, morpholinium ion, piperidinium ion, and hydroxy-(lower alkyl)-substituted ethylene-diammonium ion,

(2) a polyglycolether selected from the group consisting of fatty alcohols and saturated fatty acids having 8 to 14 carbon atoms, each mol of which is condensed with 4 to 12 equivalents of ethylene oxide, and

(3) an amide of a saturated aliphatic monocarboxylic acid having from 8 to 14 carbon atoms and a member selected from the group consisting of monoand di-hydroxy-lower alkylamines and lower alkyl ethers thereof,

the weight ratio of (1) to (2) ranging from about 12:1 to1z3, and the weight ratio (3) to the mixture of (1) and (2) being not greater than about 1:2, and

(b) adjusting the pH of the impregnation liquor to at least 5 and higher.

7. An impregnation liquor for the dyeing of polyamide fibers consisting essentially of 1) a thicker-than-water aqueous solution of an aci wool dyestuff,

(2) as color transfer agent for transferring the said acid wool dyestufi during fixing from the deposit on the fiber into the interior of the fiber, an efifective amount of a water-soluble salt of a saturated aliphatic monocarboxylic fatty acid having 8 to 14 carbon atoms with a monoto dilavent cation selected from the group consisting of alkali metal ion, ammonium ion, lower alkyl-substituted ammonium ion, hydroxy-lower alkyl-substituted ammonium ion, lower alkoxy-alkyl-substituted ammonium ion, morpholinium ion, piperidinium ion, and hydroxy-(lower alkyl) substituted ethylene diammonium ion,

(3) a polyglycolether selected from the group consisting of fatty alcohols and saturated fatty acids having 8 to 14 carbon atoms, each mol of which is condensed with 4 to 12 equivalents of ethylene oxide, the ratio of said color transfer agent to the member defined under (3) being about 1:1.

8. An impregnation liquor as defined in claim 5, wherein the effective amount of said color transfer agent is between 10 to 60 grams per liter.

9. An impregnation liquor as defined in claim 5, wherein the polyglycolether defined under (2) is present in an amount of 10 to 60 grams per liter.

10. An impregnation liquor as defined in claim 5, wherein the polyglycolether is that of a fatty alcohol having 8 to 14 carbon atoms with 4 to 6 CH -CH O groups.

11. An impregnation liquor as defined in claim 5, wherein the polyglycolether is that of a saturated fatty acid having 8 to 14 carbon atoms with 4 to 6 12. In a process for the printing of textile fiber material selected from the group consisting of woollen woven fabric and woollen yarn, which process comprises printing on the said material with a thickened printing paste containing an acid wool dyestuff and a thickener at a temperature below the drawing temperature of the dyestuff, whereby the dyestuif is deposited on the fibers of the said material without drawing on the same substantively, and then steaming the printed material in a humid medium, and thereby fixing the dyestuff on the fiber, the improvement which comprises (a) adding to the printing paste prior to the printing of the said material therewith 1) as color transfer agent for transferring the said acid wool dyestuif during steaming from the deposit on the fiber into the interior of the fibers, an effective amount of a water-soluble salt of a saturated aliphatic monocarboxylic acid having 8 to 14 carbon atoms with a monoto divalent cation selected from the group con sisting of alkali metal ion, ammonium.;,ion, lower alkyl-substituted ammonium ion, hydroxy-lower alkyl-substituted ammonium ion, lower alkoxy-alkyl-substituted ammonium ion, morpholinium ion, piperidinium ion, and hydroxy-(lower alkyl)-su*bstituted ethylene-diammonium ion, and

(2) a polyglycolether selected from the group consisting of fatty alcohols and saturated fatty acids having 8 to 14 carbon atoms, each mol of which is condensed with 4 to 12 equivalents of ethylene oxide,

(b) adjusting the pH of the printing paste to at least and higher,

(c) printing the aforesaid woollen material in unchlorinated condition with the resulting printing paste,

(d) drying the printed material at a temperature not exceeding 70 C., and

(e) steaming the material in a humid medium.

13. In a process for the printing of textile fiber material selected from the group consisting of woollen woven fabric and woollen yarn, which process comprises printing on the said material with a thickened printing paste containing an acid wool dyestuif and a thickener at a temperature below the drawing temperature of the dyestufi, whereby the dyestutf is deposited on the fibers of the said material without drawing on the same substantively, and then steaming the printed material in a humid medium, and thereby fixing the dyestufi on the fiber, the improvement which comprises (a) adding to the printing paste prior to the printing of the said material therewith (1) as color transfer agent for transferring the said acid wool dyestuff during steaming from the deposit on the fiber into the interior of the fiber, an effective amount of a water-soluble salt of a saturated aliphatic monocarboxylic acid having 8 to 14 carbon atoms with a monoto divalent cation selected from the group consisting of alkali metal ion, ammonium ion, lower alkyl-substituted ammonium ion, hydroxy-lower alkyl-substituted ammonium ion, lower alkoxy-alkyl-substituted ammonium ion, morpholinium ion, piperidinium ion, and hydroxy-(lower alkyl)-su'bstituted ethylene-diammonium ion,

(2) a polyglycolether selected from the group consisting of fatty alcohols and saturated fatty acids having 8 to 14 carbon atoms, each mol of which is condensed with 4 to 12 equivalents of ethylene oxide, and

(3) an amide of a saturated aliphatic monocarboxylic acid having from 8 to 14 carbon atoms and a member selected from the group consisting of monoand dihydroxy-lower alkylamines and lower alkyl ethers thereof,

the weight ratio of (1) to (2) ranging from about 12:1 to 1:3, and the weight ratio (3) to the mixture of (1) and (2) being not greater than about 1:2.

(b) adjusting the pH of the impregnation liquor to at least 5 and higher,

(0) printing the aforesaid woollen material in unchlorinated condition with the resulting printing paste,

(d) drying the printed mtaerial at a temperature not exceeding C., and

(e) steaming the material in a humid medium.

References Cited UNITED STATES PATENTS 3,097,041 7/ 1963 Lister 854 3,104,931 9/1963 Casty 8-54 1,581,946 4/1926 Herman 883 3,057,674 10/ 1962 Musser 883 2,228,369 1/ 1941 Schoeller 8-54 2,310,074 2/1943 GOtte 893 2,552,404 4/1951 Casty 854 X 3,083,069 3/ 1963 Hirsbrunner 854 3,096,139 7/1963 Hindle 884 X OTHER REFERENCES Casty: American Dyestuif Reporter, pp. 952-964, December 1960.

GEORGE F. LESMES, Primary Examiner T. J. HERBERT, JR., Assistant Examiner U.S. Cl. X.R. 855, 62, 83, 93 

